Catalysis without precious metals

Preface

List of Contributors

1. Catalysis Involving the H* Transfer Reactions of First-Row Transition Metals / John Hartung / Jack R. Norton

1.1. H* Transfer Between M-H Bonds and Organic Radicals

1.2. H* Transfer Between Ligands and Organic Radicals

1.3. H* Transfer Between M-H and C-C Bonds

1.4. Chain Transfer Catalysis

1.5. Catalysis of Radical Cydizations

1.6. Competing Methods for the Cyclization of Dienes

1.7. Summary and Conclusions

References

2. Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum / Richard R. Schrock

2.1Introduction.

2.2. Some Characteristics of Triamidoamine Complexes

2.3. Possible [HIPTN 3 N]Mo Intermediates in a Catalytic Reduction of Molecular Nitrogen

2.3.1. MoN 2 and MoN 2 -

2.3.2. Mo-N=NH

2.3.3. Conversion of Mo(N 2 ) into Mo-N=NH

2.3.4. [Mo=N-NH 2 ] +

2.3.5. Mo=N and [Mo=NH] +

2.3.6. Mo(NH 3 ) and [Mo(NH 3 ) +

2.4. Interconversion of Mo(NH 3 ) and Mo(N 2 )

2.5. Catalytic Reduction of Dinitrogen

2.6. MoH and Mo(H 2 )

2.7. Ligand and Metal Variations

2.8. Comments

Acknowledgements

References

3. Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis / R. Morris Bullock

3.1. Introduction

3.2. Proton Transfer Reactions of Metal Hydrides

3.3. Hydride Transfer Reactions of Metal Hydrides

3.4. Stoichiometric Hydride Transfer Reactivity of Anionic Metal Hydride Complexes

3.5. Catalytic Hydrogenation of Ketones with Anionic Metal Hydrides

3.6. Ionic Hydrogenation of Ketones Using Metal Hydrides and Added Acid

3.7. Ionic Hydrogenations from Dihydrides: Delivery of the Proton and Hydride from One Metal

3.8. Catalytic Ionic Hydrogenations With Mo and W Catalysts

3.9. Mo Phosphine Catalysts With Improved lifetimes

3.10. Tungsten Hydrogenation Catalysts with N-Heterocyclic Carbene Ligands

3.11. Catalysts for Hydrosilylation of Ketones

3.12. Cp 2 Mo Catalysts for Hydrolysis, Hydrogenations and Hydrations

3.13. Conclusion

Acknowledgements

References

4. Modern Alchemy: Replacing Precious Metals with Iron in Catalytic Alkene and Carbonyl Hydrogenation Reactions / Paul J. Chink

4.1. Introduction

4.2. Alkene Hydrogenation

4.2.1. Iron Carbonyl Complexes

4.2.2. Iron Phosphine Compounds

4.2.3. Bis(imino)pyridine Iron Complexes

4.2.4. α-Diimine Iron Complexes

4.3. Carbonyl Hydrogenation

4.3.1. Hydrosilylation

4.3.2. Bifunctional Complexes

4.4. Outlook

References

5. Olefin Oligomerizations and Polymerizations Catalyzed by Iron and Cobalt Complexes Bearing Bis(imino)pyridine Ligands / Vernon C. Gibson / Gregory A. Solan

5.1. Introduction

5.2. Precatalyst Synthesis

5.2.1. Ligand Preparation

5.2.2. Complexation with MX 2 (M = Fe, Co)

5.3. Precatalyst Activation and Catalysis

5.3.1. Olefin Polymerization

5.3.1.1. Catalytic Evaluation

5.3.1.2. Steric Versus Electronic Effects

5.3.1.3. Effect of MAO Concentration

5.3.1.4. Effects of Pressure and Temperature

5.3.1.5. α-Olefin Monomers

5.3.2. Olefin Oligomerization

5.3.2.1. Catalytic Evaluation

5.3.2.2. Substituent Effects

5.3.2.3. Schulz-Flory Distributions

5.3.2.4. Poisson Distributions

5.3.2.5. α-Olefin Monomers

5.4. The Active Catalyst and Mechanism

5.4. Active Species

5.4.1.1. Iron Catalyst

5.4.1.2. Cobalt Catalyst

5.4.2. Propagation and Chain Transfer Pathways/Theoretical Studies

5.4.3. Well-Defined Iron and Cobalt Alkyls

5.5. Other Applications

5.5.1. Immobilization

5.5.2. Reactor Blending and Tandem Catalysis

5.6. Conclusions and Outlook

References

6. Cobalt and Nickel Catalyzed Reactions Involving C-H and C-N Activation Reactions / Renee Becker / William D. Jones

6.1. Introduction

6.2. Catalysis with Cobal

6.3. Catalysis with Nickel

References

7. A Modular Approach to the Development of Molecular Electrocatalysts for H 2 Oxidation and Production Based on Inexpensive Metals / M. Rakowski DuBois / Daniel L. DuBois

7.1. Introduction

7.2. Concepts in Catalyst Design Based on Structural Studies of Hydrogenase Enzymes

7.3. A Layered or Modular Approach to Catalyst Design

7.4. Using the First Coordination Sphere to Control the Energies of Catalytic Intermediates

7.5. Using the Second Coordination Sphere to Control the Movement of Protons between the Metal and the Exterior of the Molecular Catalyst

7.6. Integration of the First and Second Coordination Spheres

7.7. Summary

Acknowledgements

References

8. Nickel-Catalyzed Reductive Couplings and Cyclizations / Hasnain A. Malik / Ryan D. Baxter / John Montgomery

8.1. Introduction

8.2. Couplings of Alkynes with α,β-Unsaturated Carbonyls

8.2.1. Three-Component Couplings via Alkyl Group Transfer-Methods Development

8.2.2. Reductive Couplings via Hydrogen Atom Transfer-Methods Development

8.2.3. Mechanistic Insights

8.2.3.1. Metallacycle-Based Mechanistic Pathway

8.2.4. Use in Natural Product Synthesis

8.3. Couplings of Alkynes with Aldehydes

8.3.1. Three-Component Couplings via Alkyl Group Transfer-Method Development

8.3.2. Reductive Couplings via Hydrogen Atom Transfer-Method Development

8.3.2.1. Simple Aldehyde and Alkyne Reductive Couplings

8.3.2.2. Directed Processes

8.3.2.3. Diastereoselective Variants: Transfer of Chirality

8.3.2.4. Asymmetric Variants

8.3.3. Mechanistic Insights

8.3.4. Cydocondensations via Hydrogen Gas Extrusion

8.3.5. Use in Natural Product Synthesis

8.4. Conclusions and Outlook

Acknowledgements

References

9. Copper-Catalyzed Ligand Promoted Ullmann-type Coupling Reactions / Yongwen Jiang / Dawei Ma

9.1. Introduction

9.2. C-N Bond Formation

9.2.1. Arylation of Amines

9.2.1.1. Arylation of Aliphatic Primary and Secondary Amines

9.2.1.2. Arylation of Aryl Amines

9.2.1.3. Arylation of Ammonia

9.2.2. Arylation and Vinylation of N-Heterocycles

9.2.2.1. Coupling of Aryl Halides and N-Heterocycles

9.2.2.2. Coupling of Vinyl Bromides and N-Heterocycles

9.2.3. Aromatic Amidation

9.2.3.1. Cross-Coupling of aryl Halides with Amides and Carbamates

9.2.3.2. Cross-Coupling of Vinyl Halides with Amides or Carbamates

9.2.3.3. Cross-Coupling of Alkynl Halides with Amides or Carbamates

9.2.4. Azidation

19.3. C-0 Bond Formation

9.3.1. Synthesis of Diaryl Ethers

9.3.2. Aryloxylation of Vinyl Halides

9.3.3. Cross-Coupling of Aryl Halides with Aliphatic Alcohols

9.4. C-C Bond Formation

9.4.1. Cross-Coupling with Terminal Acetylene

9.4.2. The Arylation of Activated Methylene Compounds

9.4.3. Cyanation

9.5. C-S Bond Formation

9.5.1. The Formation of Bisaryl- and Arylalkyl-Thioethers

9.5.2. The Synthesis of Alkenylsulfides

9.5.3. Assembly of aryl Sulfones

9.6. C-P Bond Formation

9.7. Conclusion

References

10. Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC) / M.G. Finn / Valery V. Fokin

10.1. Introduction

10.2. Azide-Alkyne Cycloaddition: Basics

10.3. Copper-Catalyzed Cycloadditions

10.3.1. Catalysts and Ligands

10.3.2. CuAAC with In Situ Generated Azides

10.3.3. Mechanistic Aspects of the CuAAC

10.3.4. Reactions of Sulfonyl Azides

10.3.5. Copper-Catalyzed Reactions with Other Dipolar Species

10.3.6. Examples of Application of the CuAAC Reaction

10.3.6.1. Synthesis of Compound libraries for Biological Screening

10.3.6.2. Copper-Binding Adhesives

10.3.7. Representative Experimental Procedures

Acknowledgements

References

11. "Frustrated Lewis Pairs": A Metal-Free Strategy for Hydrogenation Catalysis / Douglas W. Stephan

11.1. Phosphine-Borane Activation of H 2

11.2. "Frustrated Lewis Pairs"

11.3. Metal-Free Catalytic Hydxogenation

11.4. Future Considerations

Acknowledgements

References

Index